Jena Naresh K, Josefsson Ida, Eriksson Susanna K, Hagfeldt Anders, Siegbahn Hans, Björneholm Olle, Rensmo Håkan, Odelius Michael
Department of Physics, Stockholm University, AlbaNova University Center, Roslagstullsbacken 21, 106 91 Stockholm (Sweden).
Chemistry. 2015 Mar 2;21(10):4049-55. doi: 10.1002/chem.201405549. Epub 2015 Jan 28.
Ab initio molecular dynamics (MD) simulations of the solvation of LiI3 in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I3(-) ion in relation to X-ray photoelectron spectroscopy (XPS). Simulations show that hydrogen-bond rearrangement in the solvation shell is coupled to intramolecular bond-length asymmetry in the I3(-) ion. By a combination of charge analysis and I 4 d core-level XPS measurements, the mechanism of the solvent-induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent-dependent structure of the I3(-) ion, and the geometric structure has been correlated with the electronic structure.
采用从头算分子动力学（MD）模拟研究碘化锂（LiI3）在四种不同溶剂（水、甲醇、乙醇和乙腈）中的溶剂化过程，以探究I3(-)离子的分子结构和电子结构与X射线光电子能谱（XPS）的关系。模拟结果表明，溶剂化层中的氢键重排与I3(-)离子的分子内键长不对称性相关。通过电荷分析和I 4d芯能级XPS测量相结合的方法，研究了溶剂诱导畸变的机制，并得出电荷局域化介导分子间相互作用和分子内畸变的结论。这种理论与实验协同结合的方法探测了I3(-)离子的溶剂依赖性结构，并且几何结构已与电子结构相关联。
